Novel halogenated sulfides



United States Patent 3,387,034 NOVEL HALOGENATED SULFIDES Louis G. Anello, Basking Ridge, and Richard F. Sweeney, Dover, N.J., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Apr. 5, 1965, Ser. No. 445,711 14 Claims. (Cl. 260-590) ABSTRACT OF THE DISCLOSURE Novel. sulfides having the formula wherein X'X"" may be F or Cl and may be the same or different provided that there is present at least one fluorine atom and one chlorine atom in the molecule, it may be 0 or 1 and R is an aryl radical selected from the group consisting of phenyl, phenylalkyl and alkylphenyl radicals are prepared by reacting a perhalocycloalkenone of the formula wherein XX" may be P or Cl and may be the same or different provided that there is present at least one fluorine atom and one chlorine atom within X-X"", and It may be 0 or 1, with a thiol of the formula:

wherein R is an aryl radical selected from the group consisting of phenyl, phenylalkyl and alkylphenyl radicals.

The novel sulfides are useful as solvents for various polymers of trifluorochloroethylene, as sealing adjuvants for films of such polymers, and as intermediates for the preparation of fluorocarbon resins.

This invention relates to the production of a novel class of unsaturated, alicyclic, aromatic, halogen-containing ketone sulfides.

An object of this invention is to provide a novel class of chemical compounds and more particularly to provide a class of perhalocyclopentenone and cyclohexenone (aryl) sulfides, hereinafter referred to as sulfides, which sulfides are characterized by the presence of a chlorine or fluorine atom on one of the unsaturated carbon atoms of the cycloalkenone group, all of the unsatisfied valences of the saturated cyclic carbon atoms being perhalogenated with either fluorine or chlorine atoms, there being present at least one fluorine atom and one chlorine atom in the molecule.

Another object of the invention is to provide a process for the production of the above-described sulfides.

Other objects and advantages of the invention will become apparent from a consideration of the following description and discussion of the subject invention.

Patented June 4, 1968 ICC consisting of phenyl, phenylalkyl and alkylphenyl radicals.

It has been found that the above-described sulfides are useful as solvents for polymers, terpolymers and copolymers of trifluorochloroethylene and as sealing adjuvants for films of such polymers.

The novel sulfides are also useful as intermediates for the preparation of other compounds, such as synthetic resins and polymers and additionally may be used as a means of introducing fluorocarbon radicals into compounds of various structures, thereby imparting valuable characteristics thereto.

The sulfides of the invention may be prepared by reacting a perhalocycloalkenone of the formula:

XII/2C X11 4:

wherein XX" may be P or Cl and may be the same or different provided that there is present at least one fluorine atom and one chlorine atom within X'-X", and it may be 0 or 1, with a thiol of the formula:

wherein R is an 'aryl radical selected from the group consisting of phenyl, phenylalkyl and alkylphenyl radicals. There is no criticality in the number of carbon atoms which may be contained in the aryl radical R. The only limitation is the practical one of stability of the resulting thiol molecule in the reaction medium to be employed. Because of resulting stability and ease of preparation, aryl radicals of the type indicated which possess from 6-12 carbon atoms, inclusive, are preferred.

The reaction may be carried out with or without a solvent. If a solvent is employed, any of the well known inert polar solvents may be used, dioxane, diglyme and dirnethylforrnamide, being exemplary.

The reaction may be illustrated by the following equation:

wherein X and X may be P or Cl and R is as defined above. It will be noted that the initial reaction takes place at the site of the most reactive halogen atom, viz. X. Initial reaction will take place at this site regardless of whether X is a fluorine atom and X is a chlorine atom, or vice-versa.

Where other perhalocyclohexenone (aryl) sulfides and the corresponding perhalocyclopentenone (aryl) sulfides are desired, the corresponding perhalocycloalkenones are employed as starting materials and the reaction proceeds cut was redistilled, purified and identified as being subsubstantially in the same way. stantially 2 chloro-3-oxohexafluoro-l-cyclohexene(2-hy- The perhalocycloalkenone starting materials may be dro-3-oxohexafluoro-l-cyclohexene) sulfide, as described prepared by reacting the corresponding perhalocycloin Example 1 of co-pending, commonly assigned applicaalkene with sulfur trioxide in the presence of a boron or tion of Louis G. Anello and Richard F. Sweeney, Ser. No. pentavalent antimony compound catalyst at temperatures 445,709, filed Apr. 5, 1965. The high boiler was redistilled between about 50100 C., as substantially disclosed and on a small spinning band column to give 5.4 g. of a subclaimed in co-pending, commonly assigned application stantially colorless oil boiling between 117-119 C./1 of Melvin M. Schlechter and Richard F. Sweeney, Ser. No. mm. The colorless oil was purified by means of gas 373,058, filed June 5, 1964, now Patent No. 3,333,002. chromtaography and was identified by analysis to be 2- The thiol reactants (R-SH) may be prepared, as is chloro 3 oxohexafiuoro-l-cyclohexene(benzylthio)sulknown in the art, by the reaction of the corresponding fide.

aryl halides with sodium or potassium hydrosulfide. Al- Analysis.-Calculated for C ClF I-I OS, percent: C,

ternatively, such materials may be prepared indirectly 43.33; H, 1.94; S, 8.88; Cl, 9.86. Found, percent: C, 43.1;

by reaction of the corresponding aryl halides with thio- H, 1.94;S, 8.62;Cl, 9.48.

urea to produce the corresponding S-aryl isothiouronium Infrared spectrographic analysis showed a carbonyl absalts, which in turn may be hydrolyzed to the correspondsor-ption band at 5.8 microns, an SC=CCl absorption ing thiols with NaOH. band at 6.55 microns and a hydrogen absorption band at The reaction of the invention may be carried out in 3.0 microns, thus substantiating the expected structure. conventional vessels constructed of ordinary materials, E m 1 2 such as Pyrex or steel, which vessels are preferably Xa P e equipped with stirring means, condensing means and A 100 ml. Pyrex flask, equipped with a reflux condenmeans for adding the thiol reactant slowly, such as a dropser, dropping funnel, thermometer and stirrer is charged ping funnel. with 76 g. (0.30 mole) of 2,3-dichlorotetrafluoro-2-cyclo- The process afiords the advantages of operation at atpentenone (BAP. 127 C.) and 38 g. (0.31 mole) of benmospheric pressures and at low temperatures. Superatzenemethanethiol (B.P. 194 C.). The mixture is heated mospheric or subatmospheric pressures may be employed, to about 127C. and refluxed for about 64 hours during however, with no particular benefit. which time the temperature rises to about 139C. At the The reaction may be carried out over a relatively wide end of this period, the reaction product mixture is fracrange of temperatures. Those temperatures between about tionally distilled to effect recovery of about 38 g. (0.17 room temperature and the reflux temperature of the reacmole) of 2,3-dichlorotetrafiuoro-2-cyclopentenone, about tion mixture are generally preferred, although tempera- 8 g. (0.06 mole) of benezenemethanethiol reactant, about tures above and below this range are operable. Optimum 7 g. of a forecut and about 9.5 g. of a high boiler. The reaction temperatures lie between about 100 C. and the forecut is redistilled, purified and identified as 'being subrefiux temperature of the reaction mixture. stantially 2-chloro-3-oxotetrafluoro-l-cyclopentene (2-hy- Stoichiometry of the reaction requires one mole of dro-3-oxotetrafluoro-l-cyclopentene) sulfide, as described perhalocycloalkenone starting material per mole of thiol in Example 2 of co-pending application Ser. No. 445,709, reactant. The reaction will proceed with mole ratios of noted supra. The high boiler is redistilled on a small spinreactants above or below the 1:1 ratio, however, with ning band column to give about 4.3 g. of a colorless oil. proportionately diminished yields based upon the reactant 40 The colorless oil is purified by means of gas chromatopresent in excess. graphy and is identified by analysis to be 2-chloro-3- The products may be purified and recovered by ordioxotetrafluoro-l-cyclopentene(benzylthio)sulfide. gag laboratory procedures, such as fractional drstilla- Examples The products and process of the invention are further The process of Example 1 is repeated with the reactants illustrated by the following examples in which parts and listed in the indicated columns of Table I. The correspondpercentages are by weight unless otherwise indicated. ing sulfide products obtained are listed oppositely. In all of the examples, approximately a 1:1 molar ratio of thiol reactant to perhalocycloalkenone starting material is A 100 ml. Pyrex flask, equipped with a reflux eonemployed.

Example 1 TABLE I Example Perhaloeycloalkenone Reaetant Thlol Reaetant Sulfide Product 3 2,3,4,4-tetraehlorotetrafluoro-2-eyclohexenone Benzenethlol 2,6 fi-triehloro-3=oxotetrafluoro-l-cyclohexene- (phenylthio)sulfide.

4 2,3,4,4,6,6-hexachlorodifiuoro-Z-eyclohexenone.-.. Benzeneethanethiol 2,4,4,6,epentachloro-3-oxod1fiuoro-1-eyelohexene(phenylethylthimsulfide.

5 3,4,4-triehlorotrifluoro-Z-eyclopentenone Benzenehexanethiol 5,5diehlordii-oxotrifluoro-l-eyelopentene (phenylhexylthio)sulfide.

6 4,4-dich1orotetrafluoro-2-eyclopentenone 4-ethylbenzenemethanethiol 5,5 dichloro-3oxotrifluoro-1-eyelopentene (4-ethy1benzylthio)sulfide.

7 3,4,4,5,5-pentachloromonofluoro-Z-cyelo- 1,4 dimethylbenzenepropanethiol 4,4,5,5-tetrachloro-3-oxomonofluoro-l-eyele pentenone. pfillitgne(1,4-dimethylphenylpropyltluo) 8 2,5,5-triehlorotrlfiuoro-2-eyelopentenone zx-Cumenethiol 2,4,4-triehlor0-3-oxodifiuoro-1-eyelopentene (e-cumeny1thio)sulfide.

9 2,3,4,5-tetraehlorodifiuoro-Z-eyclopentenone 3-butylbeuzenethiol 2,4,5-trien1oro-3-oxodifiuoro-l-eyelopentene (3-buty1phenylthio)sulfide.

denser, dropping funnel, thermometer and stirrer was Example 10 gggizi g i lii l gg o 'g aig g zggi sfi g 2 chloro 3-oxohexafluoro-l-cyclohexene(benzylthio) of benzenemethanethiol (B.P. 194 C.). The mixture was l 2 chlOr'3'OXt?traflur'l'cyclopentent(benzy' heated to C. and refluxed for abcut 64 hours during th1o)sulfide and 2,6,6-tr1chloro-3-oxotetrofluoro-1-cyclowhich time the temperature rose to about At the hexene(phenylthro)sulfide are tested as sealing adjuvants end of this period, the reaction product mixture was fraefor P of thermoplastic film Composed of a copolymer tionally distilled and there were recovered 44 g. (0.17 about 96% tfifluowchlofoethylene'andabollt 4% y mole) of 2,3-dichlorohexafluoro-Z-eyclohexenone starting idem? fluorida Saturated Solutions of this P y in the material, 8 g. (0.06 mole) of benzenemethanethiol reactrespective sulfides are prepared by separately refluxing the ant, 9 g. of a forecut and 12 g. of a high boiler. The foresulfides with said polymer, cooling the resulting mixtures to room temperatures and decanting the respective solutions from the undissolved polymer. A pair of polymer film strips is sealed together without the use of sealing adjuvant. Three more pairs of polymer film strips are sealed together, this time employing as sealing adjuvants each of the above-described polymer solutions in the various sulfides. The sealing adjuvants are applied by merely coating, as by brushing, the inner surfaces of the film strips to be sealed. An impulse heat sealer is used. The implse heat sealer is a Sentinel Impulse Sealer manufactured by Packaging Industries, Inc., of Montclair, N. J. Sealing pressure is 30 psi. The heat sealing temperature is 400F. The dwell time for the seal, or in other words, the length of time during which the pressure and heat are applied to effect the seal, is three (3) seconds. The seal strength is tested by measuring the amount of force needed to rupture or pull apart the seal. As can be seen from the following table, the polymer film strip pairs sealed with the adjuvant solutions, rupture at weights considerably higher than the polymer film strip pair which is sealed without the use of sealing adjuvant.

TABLE II Weight to effect rupture, g.

Film strips heat-sealed without the use of adjuvant 346 Film strips heat-sealed with a polymer solution in 2-chloro-3-oxohexafiuor-o-cyclohexene ('benzylthio)sulfide 800 in 2-chloro-3-oxotetrafluorol-cyclopentene(benzylthio)sulfide 800 in 2,6,6 trichloro-3-oxotetralluoro-l-cyclohexene (phenylthio)sulfide 800 Although-a copolymer of about 96% trifluoro-chloroethylene and about 4% vinylidene fluoride is employed in the above examples, a wide variety of polymers terpolymers and copolymers of trifiuorochloroethylene may be employed with equivalent results; homoplymeric trifluorochloroethylene and copolymers of trifluorochloroethylene with vinyl chloride, 1,1-chlorofluoroethylene, trifluoroethylene and perfluorobutadiene being exemplary. In general, most suitable are those compositions containing upwards of 50% by weight of trifluorochloroethylene. The general class of compositions described above can be referred to generically as polytrifiuorochloroethylene.

When other sulfide products within the scope of the invention, such as those additional ones listed in the last column of Table I, are used as sealing adjuvants for films of polytrifiuorochloroethylene, substantially the same results are obtained; that is to say, films of polytrifiuorochloroethylene which are heat sealed employing such adjuvants rupture at weights considerably higher than films of polytrifiuorochloroethylene which are heat sealed without using sealing adjuvants.

Since various changes and modifications may be made without departing from the spirit of the invention, the invention is to be limited only by the scope of the appended claims.

6 We claim: 1. Compounds of the formula:

C Ii/IIIi XIIVIOI O S R X w /CX' wherein XX"" may be F or Cl and may be the same or different provided that there is present at least one fluorine atom and one chlorine atom in the molecule, 12 may be 0 or 1 and R is an aryl radical selected from the group consisting of phenyl, phenylalkyl and alkylphenyl radicals.

2. Compounds according to claim 1 in which R is alkylphenyl.

3. Compounds according to claim 2 in which n is 0.

4. Compounds according to claim 2 in which n is l.

5. Compounds of the formula:

XII/2C XII2C C II 0 wherein X"-/ may be F or Cl and may be the same or different provided that there is present at least one fluorine atom in the molecule, n may be 0 or 1 and R is an aryl radical selected from the group consisting of phenyl, phenylalkyl and alkylphenyl radicals.

6. Compounds according to claim 5 in which R is phenyl.

7. Compounds according to claim 5 in which R is phenylalkyl.

8. Compounds according to claim 5 wherein R is alkylphenyl.

9. Compounds according to claim 8 in which n is 0. 10. 2-chloro-3-oxohexafluoro 1 cyclohexene(benzylthio)sulfide.

11. 2 chloro-3-oxotetrafluoro-l-cyclopentene(benzylthio)sulfide.

12. 2,6,6,-trichloro-3-oxotetrafluoro l cyclohexene phenylthio sulfide.

13. Compounds according to claim 1 in which R is phenyl.

14. Compounds according to claim 1 wherein R is pilenylalkyl.

References Cited UNITED STATES PATENTS 3,141,907 7/1964- Mark 260609 OTHER REFERENCES Weil et al., J. Org. Chem. vol. 28(9), pp. 222l-2224 (1963), QD 24l.C6.

BERNARD HELFIN, Acting Primary Examiner.

LEON ZITVER, Examiner.

M. JACOB, Assistant Examiner. 

